Dibromidobis(1-ethyl-2,6-dimethyl-pyridinium-4-olate-κO)zinc(II).

In the bioactive title compound, [ZnBr(2)(C(9)H(13)NO)(2)], the Zn(II) atom is coordinated in a distorted tetra-hedral arrangement by two Br(-) anions and the O atoms of two zwitterionic organic ligands. The pyridinium rings are almost planar [maximum deviations = 0.004 (4) and 0.003 (4) Å]. The ethyl groups are approximately perpendicular to the corresponding pyridinium ring planes [N-C-C-C = 88.8 (4)° in each ligand]. The packing of the mol-ecules is controlled by π-π inter-actions, with centroid-centroid distances of 3.625 (3) and 3.711 (2) Å, forming chains approximately parallel to (102). The crystal studied was non-merohedrally twinned (twin relationship between the domains 1 0 0, 0 1 0, -0.4672 -0.1864 -1 and batch scale factor of 7.39%).

Related literature

For general background to pyridinium compounds and their applications, see: Darensbourg et al. (2003 ▶); Dhanuskodi et al. (2006 ▶); Glavcheva et al. (2004 ▶); Lakshmanaperumal et al. (2002 ▶, 2004 ▶); Usman et al. (2000 ▶, 2001 ▶); Mootz & Wusson (1981 ▶). For their biological activity, see: Akkurt et al. (2005 ▶). For related structures, see: Thenmozhi et al. (2010 ▶); Mootz & Wusson (1981 ▶); Sundar et al. (2004 ▶). For the preparation of the ligand, see: Garratt (1963 ▶).

Experimental

Crystal data

[ZnBr2(C9H13NO)2]

M = 527.60

Triclinic,

a = 8.462 (1) Å

b = 8.518 (1) Å

c = 14.418 (3) Å

α = 93.131 (6)°

β = 97.871 (7)°

γ = 90.210 (8)°

V = 1027.9 (2) Å3

Z = 2

Mo Kα radiation

μ = 5.10 mm−1

T = 293 K

0.12 × 0.11 × 0.11 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T min = 0.580, T max = 0.604

16553 measured reflections

16553 independent reflections

13614 reflections with I > 2σ(I)

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.189

S = 1.06

16553 reflections

233 parameters

H-atom parameters constrained

Δρmax = 1.20 e Å−3

Δρmin = −0.95 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810052190/sj5050sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810052190/sj5050Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[ZnBr2(C9H13NO)2]	Z = 2
Mr = 527.60	F(000) = 528
Triclinic, P1	Dx = 1.705 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.462 (1) Å	Cell parameters from 16553 reflections
b = 8.518 (1) Å	θ = 1.4–25.0°
c = 14.418 (3) Å	µ = 5.10 mm−1
α = 93.131 (6)°	T = 293 K
β = 97.871 (7)°	Block, colourless
γ = 90.210 (8)°	0.12 × 0.11 × 0.11 mm
V = 1027.9 (2) Å3

Bruker Kappa APEXII area-detector diffractometer	16553 independent reflections
Radiation source: fine-focus sealed tube	13614 reflections with I > 2σ(I)
graphite	Rint = 0.000
ω and φ scans	θmax = 25.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −10→10
Tmin = 0.580, Tmax = 0.604	k = −10→10
16553 measured reflections	l = −17→17

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.189	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0512P)2 + 13.5867P] where P = (Fo2 + 2Fc2)/3
16553 reflections	(Δ/σ)max < 0.001
233 parameters	Δρmax = 1.20 e Å−3
0 restraints	Δρmin = −0.95 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C2	1.2061 (5)	0.5686 (6)	0.1164 (3)	0.0379 (11)
C3	1.1571 (5)	0.4291 (5)	0.1424 (3)	0.0369 (11)
H3	1.2321	0.3503	0.1536	0.044*
C4	0.9992 (5)	0.3972 (5)	0.1532 (3)	0.0350 (10)
C5	0.8909 (5)	0.5207 (5)	0.1318 (3)	0.0372 (11)
H5	0.7830	0.5052	0.1351	0.045*
C6	0.9418 (5)	0.6608 (6)	0.1066 (3)	0.0383 (11)
C7	1.1564 (7)	0.8459 (6)	0.0842 (4)	0.0565 (15)
H7A	1.0751	0.8990	0.0437	0.068*
H7B	1.2507	0.8371	0.0530	0.068*
C8	1.1965 (8)	0.9428 (7)	0.1766 (5)	0.080 (2)
H8A	1.1046	0.9476	0.2089	0.120*
H8B	1.2276	1.0473	0.1642	0.120*
H8C	1.2828	0.8946	0.2149	0.120*
C9	1.3764 (6)	0.5978 (6)	0.1057 (4)	0.0535 (14)
H9A	1.4400	0.5118	0.1293	0.080*
H9B	1.4132	0.6935	0.1404	0.080*
H9C	1.3858	0.6069	0.0406	0.080*
C10	0.8236 (6)	0.7901 (7)	0.0860 (4)	0.0620 (16)
H10A	0.7186	0.7529	0.0922	0.093*
H10B	0.8256	0.8212	0.0231	0.093*
H10C	0.8513	0.8786	0.1293	0.093*
C12	0.4359 (5)	0.6653 (5)	0.3969 (3)	0.0337 (10)
C13	0.5639 (5)	0.6198 (5)	0.3569 (3)	0.0360 (10)
H13	0.6383	0.6954	0.3469	0.043*
C14	0.5894 (5)	0.4615 (5)	0.3295 (3)	0.0339 (10)
C15	0.4688 (5)	0.3538 (5)	0.3449 (3)	0.0331 (10)
H15	0.4788	0.2481	0.3273	0.040*
C16	0.3392 (5)	0.4008 (5)	0.3848 (3)	0.0317 (9)
C17	0.1813 (5)	0.6083 (6)	0.4556 (3)	0.0429 (11)
H17A	0.2108	0.6970	0.4997	0.051*
H17B	0.1447	0.5237	0.4900	0.051*
C18	0.0477 (6)	0.6553 (7)	0.3824 (4)	0.0587 (15)
H18A	0.0911	0.7110	0.3353	0.088*
H18B	−0.0248	0.7219	0.4114	0.088*
H18C	−0.0081	0.5628	0.3538	0.088*
C19	0.4154 (6)	0.8323 (6)	0.4274 (4)	0.0537 (14)
H19A	0.4116	0.8405	0.4938	0.080*
H19B	0.3178	0.8707	0.3950	0.080*
H19C	0.5036	0.8937	0.4133	0.080*
C20	0.2141 (6)	0.2841 (6)	0.3993 (4)	0.0513 (13)
H20A	0.2376	0.1835	0.3714	0.077*
H20B	0.1118	0.3182	0.3706	0.077*
H20C	0.2124	0.2755	0.4653	0.077*
O1	0.9580 (4)	0.2656 (4)	0.1836 (3)	0.0475 (9)
O2	0.7136 (4)	0.4211 (4)	0.2935 (2)	0.0429 (8)
Zn1	0.75971 (6)	0.21641 (6)	0.23222 (4)	0.03594 (15)
Br1	0.81438 (7)	0.03353 (6)	0.34965 (4)	0.05785 (18)
Br2	0.55242 (6)	0.15373 (7)	0.10973 (4)	0.05343 (17)
N1	1.0984 (4)	0.6872 (4)	0.1000 (2)	0.0371 (9)
N11	0.3231 (4)	0.5561 (4)	0.4125 (2)	0.0315 (8)

	U11	U22	U33	U12	U13	U23
C2	0.029 (2)	0.051 (3)	0.035 (2)	0.007 (2)	0.0074 (19)	0.008 (2)
C3	0.034 (2)	0.044 (3)	0.035 (2)	0.010 (2)	0.0085 (19)	0.011 (2)
C4	0.030 (2)	0.035 (3)	0.042 (3)	−0.0005 (19)	0.0070 (19)	0.006 (2)
C5	0.026 (2)	0.047 (3)	0.038 (3)	0.005 (2)	0.0040 (19)	0.002 (2)
C6	0.034 (2)	0.042 (3)	0.039 (3)	0.014 (2)	0.003 (2)	0.008 (2)
C7	0.060 (3)	0.044 (3)	0.073 (4)	0.011 (3)	0.026 (3)	0.029 (3)
C8	0.087 (5)	0.050 (4)	0.112 (6)	−0.017 (3)	0.045 (4)	0.004 (4)
C9	0.039 (3)	0.055 (3)	0.072 (4)	0.007 (2)	0.023 (3)	0.021 (3)
C10	0.044 (3)	0.055 (4)	0.091 (5)	0.020 (3)	0.013 (3)	0.026 (3)
C12	0.039 (3)	0.028 (2)	0.034 (2)	0.0002 (19)	0.0043 (19)	0.0002 (19)
C13	0.036 (2)	0.029 (2)	0.044 (3)	−0.0046 (19)	0.008 (2)	0.000 (2)
C14	0.033 (2)	0.033 (2)	0.035 (2)	−0.0012 (19)	0.0053 (19)	−0.0052 (19)
C15	0.041 (3)	0.028 (2)	0.029 (2)	0.0029 (19)	0.0046 (19)	−0.0016 (18)
C16	0.032 (2)	0.031 (2)	0.030 (2)	−0.0044 (18)	−0.0020 (18)	−0.0008 (18)
C17	0.038 (3)	0.048 (3)	0.044 (3)	0.004 (2)	0.013 (2)	−0.004 (2)
C18	0.043 (3)	0.077 (4)	0.058 (3)	0.014 (3)	0.010 (3)	0.006 (3)
C19	0.055 (3)	0.031 (3)	0.075 (4)	−0.002 (2)	0.017 (3)	−0.009 (3)
C20	0.049 (3)	0.038 (3)	0.071 (4)	−0.013 (2)	0.023 (3)	−0.001 (3)
O1	0.0378 (18)	0.040 (2)	0.070 (2)	0.0061 (15)	0.0231 (17)	0.0082 (17)
O2	0.0421 (19)	0.0312 (18)	0.058 (2)	0.0000 (14)	0.0203 (16)	−0.0084 (15)
Zn1	0.0333 (3)	0.0302 (3)	0.0456 (3)	0.0014 (2)	0.0118 (2)	−0.0023 (2)
Br1	0.0676 (4)	0.0476 (3)	0.0622 (4)	0.0091 (3)	0.0173 (3)	0.0164 (3)
Br2	0.0441 (3)	0.0648 (4)	0.0494 (3)	−0.0022 (2)	0.0027 (2)	−0.0056 (3)
N1	0.041 (2)	0.038 (2)	0.034 (2)	0.0061 (17)	0.0099 (17)	0.0120 (17)
N11	0.0326 (19)	0.031 (2)	0.0302 (19)	−0.0020 (15)	0.0055 (15)	−0.0048 (15)

C2—C3	1.347 (6)	C12—C19	1.484 (6)
C2—N1	1.371 (5)	C13—C14	1.410 (6)
C2—C9	1.492 (6)	C13—H13	0.9300
C3—C4	1.395 (6)	C14—O2	1.275 (5)
C3—H3	0.9300	C14—C15	1.418 (6)
C4—O1	1.289 (5)	C15—C16	1.358 (6)
C4—C5	1.417 (6)	C15—H15	0.9300
C5—C6	1.352 (6)	C16—N11	1.374 (5)
C5—H5	0.9300	C16—C20	1.493 (6)
C6—N1	1.360 (6)	C17—N11	1.483 (5)
C6—C10	1.504 (6)	C17—C18	1.508 (7)
C7—N1	1.476 (6)	C17—H17A	0.9700
C7—C8	1.525 (9)	C17—H17B	0.9700
C7—H7A	0.9700	C18—H18A	0.9600
C7—H7B	0.9700	C18—H18B	0.9600
C8—H8A	0.9600	C18—H18C	0.9600
C8—H8B	0.9600	C19—H19A	0.9600
C8—H8C	0.9600	C19—H19B	0.9600
C9—H9A	0.9600	C19—H19C	0.9600
C9—H9B	0.9600	C20—H20A	0.9600
C9—H9C	0.9600	C20—H20B	0.9600
C10—H10A	0.9600	C20—H20C	0.9600
C10—H10B	0.9600	O1—Zn1	1.957 (3)
C10—H10C	0.9600	O2—Zn1	1.976 (3)
C12—C13	1.344 (6)	Zn1—Br2	2.3501 (8)
C12—N11	1.379 (5)	Zn1—Br1	2.3635 (8)
C3—C2—N1	119.8 (4)	O2—C14—C15	123.5 (4)
C3—C2—C9	121.2 (4)	C13—C14—C15	115.4 (4)
N1—C2—C9	119.0 (4)	C16—C15—C14	121.9 (4)
C2—C3—C4	123.0 (4)	C16—C15—H15	119.1
C2—C3—H3	118.5	C14—C15—H15	119.1
C4—C3—H3	118.5	C15—C16—N11	120.0 (4)
O1—C4—C3	121.4 (4)	C15—C16—C20	120.3 (4)
O1—C4—C5	123.3 (4)	N11—C16—C20	119.7 (4)
C3—C4—C5	115.3 (4)	N11—C17—C18	111.4 (4)
C6—C5—C4	121.1 (4)	N11—C17—H17A	109.3
C6—C5—H5	119.4	C18—C17—H17A	109.3
C4—C5—H5	119.4	N11—C17—H17B	109.3
C5—C6—N1	121.1 (4)	C18—C17—H17B	109.3
C5—C6—C10	119.5 (4)	H17A—C17—H17B	108.0
N1—C6—C10	119.4 (4)	C17—C18—H18A	109.5
N1—C7—C8	111.1 (4)	C17—C18—H18B	109.5
N1—C7—H7A	109.4	H18A—C18—H18B	109.5
C8—C7—H7A	109.4	C17—C18—H18C	109.5
N1—C7—H7B	109.4	H18A—C18—H18C	109.5
C8—C7—H7B	109.4	H18B—C18—H18C	109.5
H7A—C7—H7B	108.0	C12—C19—H19A	109.5
C7—C8—H8A	109.5	C12—C19—H19B	109.5
C7—C8—H8B	109.5	H19A—C19—H19B	109.5
H8A—C8—H8B	109.5	C12—C19—H19C	109.5
C7—C8—H8C	109.5	H19A—C19—H19C	109.5
H8A—C8—H8C	109.5	H19B—C19—H19C	109.5
H8B—C8—H8C	109.5	C16—C20—H20A	109.5
C2—C9—H9A	109.5	C16—C20—H20B	109.5
C2—C9—H9B	109.5	H20A—C20—H20B	109.5
H9A—C9—H9B	109.5	C16—C20—H20C	109.5
C2—C9—H9C	109.5	H20A—C20—H20C	109.5
H9A—C9—H9C	109.5	H20B—C20—H20C	109.5
H9B—C9—H9C	109.5	C4—O1—Zn1	127.6 (3)
C6—C10—H10A	109.5	C14—O2—Zn1	128.4 (3)
C6—C10—H10B	109.5	O1—Zn1—O2	101.12 (13)
H10A—C10—H10B	109.5	O1—Zn1—Br2	111.24 (11)
C6—C10—H10C	109.5	O2—Zn1—Br2	108.65 (10)
H10A—C10—H10C	109.5	O1—Zn1—Br1	108.88 (10)
H10B—C10—H10C	109.5	O2—Zn1—Br1	108.20 (10)
C13—C12—N11	120.3 (4)	Br2—Zn1—Br1	117.46 (3)
C13—C12—C19	120.9 (4)	C6—N1—C2	119.7 (4)
N11—C12—C19	118.8 (4)	C6—N1—C7	120.7 (4)
C12—C13—C14	122.4 (4)	C2—N1—C7	119.4 (4)
C12—C13—H13	118.8	C16—N11—C12	120.0 (3)
C14—C13—H13	118.8	C16—N11—C17	120.3 (4)
O2—C14—C13	121.1 (4)	C12—N11—C17	119.7 (4)
N1—C2—C3—C4	0.5 (7)	C14—O2—Zn1—O1	172.7 (4)
C9—C2—C3—C4	179.9 (5)	C14—O2—Zn1—Br2	55.6 (4)
C2—C3—C4—O1	−175.8 (5)	C14—O2—Zn1—Br1	−72.9 (4)
C2—C3—C4—C5	2.1 (7)	C5—C6—N1—C2	2.1 (7)
O1—C4—C5—C6	175.2 (5)	C10—C6—N1—C2	−178.3 (5)
C3—C4—C5—C6	−2.7 (7)	C5—C6—N1—C7	−172.2 (5)
C4—C5—C6—N1	0.7 (7)	C10—C6—N1—C7	7.4 (7)
C4—C5—C6—C10	−178.9 (5)	C3—C2—N1—C6	−2.6 (7)
N11—C12—C13—C14	−0.2 (7)	C9—C2—N1—C6	177.9 (4)
C19—C12—C13—C14	178.2 (5)	C3—C2—N1—C7	171.7 (5)
C12—C13—C14—O2	−178.5 (4)	C9—C2—N1—C7	−7.7 (7)
C12—C13—C14—C15	1.5 (7)	C8—C7—N1—C6	85.7 (6)
O2—C14—C15—C16	179.0 (4)	C8—C7—N1—C2	−88.6 (5)
C13—C14—C15—C16	−1.0 (6)	C15—C16—N11—C12	2.2 (6)
C14—C15—C16—N11	−0.8 (6)	C20—C16—N11—C12	−178.2 (4)
C14—C15—C16—C20	179.6 (4)	C15—C16—N11—C17	179.7 (4)
C3—C4—O1—Zn1	164.0 (3)	C20—C16—N11—C17	−0.8 (6)
C5—C4—O1—Zn1	−13.8 (7)	C13—C12—N11—C16	−1.8 (6)
C13—C14—O2—Zn1	−169.5 (3)	C19—C12—N11—C16	179.9 (4)
C15—C14—O2—Zn1	10.5 (6)	C13—C12—N11—C17	−179.2 (4)
C4—O1—Zn1—O2	−33.4 (4)	C19—C12—N11—C17	2.5 (6)
C4—O1—Zn1—Br2	81.8 (4)	C18—C17—N11—C16	−89.8 (5)
C4—O1—Zn1—Br1	−147.2 (4)	C18—C17—N11—C12	87.6 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2	0.93	2.57	3.093 (5)	116.

Table 1

Selected bond lengths (Å)

O1—Zn1	1.957 (3)
O2—Zn1	1.976 (3)
Zn1—Br2	2.3501 (8)
Zn1—Br1	2.3635 (8)